737 resultados para Polymer Nanocomposites
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Objective: The purpose of this study was to evaluate the sealing ability of castor oil polymer (COP), mineral trioxide aggregate (MTA) and glass ionomer cement (GIC) as root-end filling materials. Forty-five single-rooted human teeth were cleaned and prepared using a step-back technique. The apical third of each root was resected perpendicularly to the long axis direction. All teeth were obturated with gutta-percha and an endodontic sealer. After, a root-end cavity with 1.25-mm depth was prepared using a diamond bur. The specimens were randomly divided into three experimental groups (n = 15), according to the root-end filling material used: G1) COP; G2) MTA; G3) GIC. The external surfaces of the specimens were covered with epoxy adhesive, except the root-end filling. The teeth were immersed in rhodamine B dye for 24 hours. Then, the roots were sectioned longitudinally and the linear dye penetration at the dentin/material interface was determined using a stereomicroscope. ANOVA and Tukey's tests were used to compare the three groups. The G1 group (COP) presented smaller dye penetration, statistically different than the G2 (MTA) and G3 (GIC) groups (p < 0.05). No statistically significant difference in microleakage was observed between G2 and G3 groups (p > 0.05). The results of this study indicate that the COP presented efficient sealing ability when used as a root-end filling material showing results significantly better than MTA and GIC.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes
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The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Small-angle X-ray scattering study of sol-gel-derived siloxane-PEG and siloxane-PPG hybrid materials
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Hybrid organic-inorganic two-phase nanocomposites of siloxane-poly(ethylene glycol) (SiO3/2-PEG) and siloxane-poly(propylene glycol) (SiO3/2-PPG) have been obtained by the sol-gel process. In these composites, nanometric siloxane heterogeneities are embedded in a polymeric matrix with covalent bonds in the interfaces. The structure of these materials was investigated in samples with different molecular weights of the polymer using the smalt-angle X-ray scattering (SAXS) technique. The SAXS spectra exhibit a well-defined peak that was attributed to the existence of a strong spatial correlation of siloxane clusters. LiClO4-doped siloxane-PEG and siloxane-PPG hybrids, which exhibit good ionic conduction properties, have also been studied as a function of the lithium concentration [O]/[Li], O being the oxygens of ether type. SAXS results allowed us to establish a structural model for these materials for different basic compositions and a varying [Li] content. The conclusion is consistent with that deduced from ionic conductivity measurements that exhibit a maximum for [O]/[Li] =15.
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Hybrid transparent and flexible siloxane-polypropyleneglycol (PPG) materials with covalent bonds between the inorganic (siloxane) and organic (polymeric) phases were prepared by sol-gel process. In order to improve the quality of the mechanical properties of these materials, different amounts of methyltriethoxysilane (MTES) were added to the initial sol. The effect of MTES addition on the structure of the composites was studied by Small-Angle X-Ray Scattering (SAXS) and Si-29 Nuclear Magnetic Resonance (Si-29 NMR). In absence of MTES, SAXS spectra exhibit a peak that is assigned to spatial correlation due to short range order between the siloxane clusters embedded in the polymeric phase. The experimental results indicate that, for low MTES concentrations ([MTES]/[O] less than or equal to 0.8, O: ether-type oxygen of PPG), the silicon species resulting from hydrolysis and condensation of MTES fill the open spaces between polymeric chains, interacting with the ether-type oxygens. For larger MTES content ([MTES]/[O] greater than or equal to 0.8), the number of free ether-type oxygen sites avalaible for reaction with such silicon species is not large enough. Consequently, a fraction of silicon species resulting from MTES addition graft to siloxane clusters formed by hydrolysis and condensation of the hybrid precursor. For all MTES concentrations the condensation degree of the siloxane phase, determined from Si-29 NMR spectroscopy, is high (> 69%), as expected under neutral pH synthesis conditions.
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The modelling of the local structure of sol-gel derived Eu3+-based organic/inorganic hybrids is reported, based on Small-Angle X-ray Scattering (SAXS), photoluminescence and mid-infrared spectroscopy. The hybrid matrix of these organically modified silicates, classed as di-ureasils and termed U(2000) and U(600), is formed by poly( oxyethylene) (POE) chains of variable length grafted to siloxane domains by means of urea cross-linkages. Europium triflate, Eu(CF3SO3)(3), was incorporated in the two di-ureasil matrices with compositions 400 greater than or equal ton greater than or equal to 10, n is the molar ratio of ether oxygens per Eu3+. The SAXS data for undoped hybrids (n=infinity) show the presence of a well-defined peak attributed to the existence of a liquid-like spatial correlation of siloxane rich domains embedded in the polymer matrix and located at the ends of the organic segments. The obtained siloxane particle gyration radius Rg(1) is around 5 Angstrom (error within 10%), whereas the interparticle distance d is 25 +/-2 Angstrom and 40 +/-2 Angstrom, for U(600) and U(2000), respectively. For the Eu3+-based nanocomposites the formation of a two-level hierarchical local structure is discerned. The primary level is constituted by strongly spatially correlated siloxane particles of gyration radius Rg(1) (4-6 and 3-8 Angstrom, errors within 5%, for U(600())n Eu(CF3SO3)(3), 200 greater than or equal ton greater than or equal to 40, and U(2000)(n)Eu(CF3SO3)(3), 400 greater than or equal ton greater than or equal to 40, respectively) forming large clusters of gyration radius Rg(2) (approximate to 75 +/- 10 Angstrom). The local coordination of Eu3+ in both di-ureasil series is described combining the SAXS, photoluminescence and mid-infrared results. In the di-ureasils containing long polymer chains, U(2000)(n)Eu(CF3SO3)(3), the cations interact exclusively with the carbonyl oxygens atoms of the urea bridges at the siloxane-POE interface. In the hybrids containing shorter chains, U(600)(n)Eu(CF3SO3)(3) with n ranging from 200 to 60, the Eu3+ ions interact solely with the ether-type oxygens of the polymer chains. Nevertheless, in this latter family of hybrids a distinct Eu3+ local site environment involving the urea cross-linkages is detected when the europium content is increased up to n=40.
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Hybrid siloxane-polymethylmethacrylate (PMMA) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (polymer) phases were prepared by the sot gel process through hydrolysis and polycondensation of 3-(trimethoxysilyl)propylmethacrylate (TMSM) and polymerization of methylmethacrylate (MMA) using benzoyl peroxide (BPO) as initiator. The effect of MMA, BPO and water contents on the viscoelastic behaviour of these materials was analysed during gelation by dynamic rheological measurements. The changes in storage (G') and loss moduli (G), complex viscosity (eta*) and phase angle (6) were measured as a function of the reaction time showing the viscous character of the sot in the initial step of gelation and its progressive transformation to an elastic gel. This study was complemented by Si-29 and C-13 solid-state nuclear magnetic resonance (NMR/MAS) measurements of dried gel. The analysis of the experimental results shows that linear chains are formed in the initial step of the gelation followed by a growth of branched structures and formation of a three-dimensional network. Near the gel point this hybrid material demonstrates the typical scaling behaviour expected from percolation theory.